DE2247170B2 - POLYMERIZED PREPARATIONS DEGRADABLE BY ENVIRONMENTAL INFLUENCES AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

35

The present invention relates to ethylene polymer preparations, and it relates in particular to those ethylene polymer preparations which are exposed to the effects of the weather be dismantled.

From US Pat. No. 34 54 510 it is known that polyolefin films, in particular covering ("mulch") films after adding certain oxidation-promoting metal salts are degraded under the influence of the outside world; however, this applies essentially only to opaque ones Foils.

It is also known from USA patents 33 20 695 and 33 41 357 that the degradation of polyolefin films is promoted if one adds certain unsaturated hydrocarbons to the films. These opaque Foils, which are also used for covering (»mulching«) work, however, require relatively large amounts by weight of these unsaturated hydrocarbons, so that only a "soft" product is obtained, d. H. a product that is normally not considered suitable for the end user.

The present invention now creates an ethylene polymer preparation which is used for the production of translucent to clear plastic products suitable for consumers during normal Use maintains its structural stability and, after being thrown away, is degraded by external influences will. This degradation of the ethylene polymer preparation takes place considerably faster if the preparation natural or artificial actinic light is set.

It has been found that the polymer preparation according to the invention, which contains a combination of an organic additive with a tendency to autoxidation and a polyvalent transition metal salt in an ethylene polymer, weathers much more quickly than similar products which contain equivalent amounts of the self-oxidizing organic additive or the polyvalent transition salt alone. The preparations according to the invention can also be admixed with conventional additives known for ethylene polymers, such as. B. fillers, pigments, lubricants, antioxidants, antistatic agents, agents to prevent sticking or fogging.

In certain cases it has been shown that the combination of moderate amounts of a self-oxidizing organic additive and a polyvalent transition metal salt in an ethylene polymer leads to higher weathering rates than if the ethylene polymer is equivalent or even larger amounts of the individual components alone can be added.

It has been found that the products from the ethylene polymer preparations according to the invention under Weather influences form many multifaceted cracks, break apart and finally become small Particles disintegrate. Over time, this cracking continues on the small pieces, so that the Material breaks down into ever finer particles. There are no external physical to cause this disintegration Forces required; physical action can, however, "repel" the external disintegrating layers are accelerated, whereby new surfaces are exposed to the weather.

The ethylene polymer preparation according to the invention, which can be degraded by external influences, therefore consists of (I) an ethylene polymer and, as synergistic Combination of additives, (II) a self-oxidizing additive in the form of a Polymerizates or an organic compound with a low molecular weight and (III) a polyvalent one Transition metal salt; in addition, (IV) a stabilizer or an antioxidant for the Ethylene polymer be present. Under the designation "ethylene polymer preparation" is therefore in each case to understand this preparation described above.

More precisely, the ethylene polymer preparation according to the invention contains: (I) an ethylene polymer base resin and, in the form of a synergistic combination of additives, (II) a polymer or a low molecular weight organic compound, being the majority of units ("Mer units") or the organic compound has at least one hydrogen atom that is linked to a Carbon atom and shows a greater tendency to self-oxidize than one with one normal secondary carbon atom linked hydrogen atom, (III) an organic salt of a polyvalent metal, at least one metal being a transition metal in which the electron transition takes place in the 3d or 4f secondary shell, and (IV) an organic antioxidant for the ethylene polymer.

The ethylene polymer preparation according to the invention contains polyethylene, polyether or polypropylene; a organic salt of a polyvalent transition metal, the metal being iron, manganese, zinc or cobalt can be; and an antioxidant such as. B. the sterically hindered phenols, arylamines, thioureas, Thiocarbamates, phosphites and thioether esters.

Haaen antioxidants for ethylene polymers proved to be suitable for stabilizing the ethylene polymer preparations according to the invention in such a way that that the time that has passed before it becomes brittle is practically "built into" the preparation.

This is valuable in that - if the normal lifespan (time before throwing away) a The object is known - the amounts of anti-oxidants and additives can be measured in such a way that that the product is structurally stable during its normal life, but within a relatively short period of time becomes brittle as soon as it is exposed to the elements.

The ethylene polymer preparations according to the invention can be prepared by various known methods be produced, e.g. B. by direct addition of all components; by creating basic approaches, taking a single approach multiple ingredients, but not the polyvalent transition metal compound and to contain the self-oxidizing organic additive at the same time; or by others known procedures.

The production of preparations by direct addition of all components and subsequent stirring, until a homogeneous mixture is obtained is known. When working with principles be first two or more preparations are made which are then combined into a single homogeneous mixture. at This process is based on the polyvalent transition metal compound and the self-oxidizing additive initially in separate basic preparations. These preparations are then used at a later date Time combined or mixed in the correct proportions and deliver the invention Ethylene polymer preparations. In this way, the shelf life or storability of the preparations as long as these two components of the Ethylene polymer preparations have not been mixed homogeneously with one another.

So you can z. B. a first basic preparation of ethylene polymer plus polyvalent transition metal compound plus a sufficient amount of antioxidant to stabilize this basic preparation and then a second basic preparation the self-oxidizing additives, such as. B. propylene polymer or alkylene oxide polymer, with or without ethylene polymer plus one for stabilization use this second basic preparation to produce a sufficient amount of antioxidant. Also can one or both basic preparations contain the usual amounts of known additives. Farther you can also make more than two so-called basic preparations.

As long as the first and second basic preparation are stored in separate containers, the degradation described above does not occur. Even if the beads of the two basic preparations are mixed together, the mixture thus obtained shows no decomposition due to environmental pollution. This only occurs when the two or more basic preparations are fused together so that the self-oxidizing additive and the polyvalent transition metal compound are present in a single, uniform and homogeneous ethylene polymer preparation. ^(l 5

In a special embodiment of the process for producing the claimed degradable polymers tnräarate is first a basic approach of using the base resin and self-oxidizing additive a base formulation of the base resin and the salt of a polyvalent transition metal dry blended and then heated to melting and mixing continued. The antioxidant can be used be present for the base resin in at least one basic approach and the basic approaches can optionally be mixed with an additional amount of ethylene polymer. The antioxidant is preferably present in the base batch containing the metal compound.

According to a further embodiment of the invention, an inert carrier is preferably used before mixing Silicon oxide coated with the metal compound, optionally also including an oxidizing agent the inert carrier is applied.

The final mixing of the basic preparations can be done by known methods, e.g. B. by Mixing in solution or melt, rolling, processing in a Banbury mixer or a screw mixer or the like. It can also be used in the device used to manufacture the finished product take place, e.g. B. during extrusion or in a spinning process.

The ethylene polymer preparations according to the invention can be processed by known processes of ethylene polymers are usually used, for example to moldings, in particular be processed into foils, e.g. B. by extrusion, such as a combined film tube-extrusion-blow molding process, Slot extrusion of films, slot form coating extrusion; Molding such as injection molding, blowing, carousel pressing, transfer molding and the like; Fiber formation, like Melt spinning, drawing and the like.

The base resin is a normally solid thermoplastic ethylene polymer. Ethylene homopolymers can be used or copolymers in which the ethylene fraction predominates, or mixtures these polymers can be used with one another or with other polymers. According to the invention are both high density polyethylene and low density polyethylene or mixtures suitable for these materials.

The ethylene polymers used as base resins for the process according to the invention have a high Densities are generally linear in structure and are known as "linear polyethylenes". It is It is known that very dense linear polyethylenes contain chain transfer agents and / or chain terminating agents can be added to increase melt viscosity, molecular weight or other properties to modify the resin, and these modified polymers are of the present Invention includes. High density polyethylenes generally have a density of 0.94 g / cc or more on, e.g. B. a density between 0.94 g / ccm and about 0.97 g / ccm. The melt index of such polyethylene high density can be between 0.005 and 100 dg / min, preferably between 0.15 and 50 dg / min. (ASTM method D-1238). It should be noted, however, that mixtures are also more highly dense Polyethylene can be used as the base resin for the ethylene polymer preparations according to the invention and that the melt index of these mixtures can be below 0.005 dg / min, or more than 100 dg / m in.

Ethylene homopolymers with a low density are characterized by a density of less than 0.94 g / ccm

marked, ζ. Β. by densities between 0.91 and 0.93 g / ccm. These ethylene homopolymers with less Density shows melt indices between about 0.05 dg / min, and about 100 dg / min, preferably between 0.5 and 20 dg / min .; if appropriate, mixtures of these polymers can also be used will.

Ethylene copolymers suitable as base resins for the process according to the invention are made by Interpolymerization of ethylene with a monomer obtained from the group

I I —C = c—

which can be copolymerized with ethylene and a thermoplastic copolymer supplies. Examples of such copolymerizable monomers are the olefins (in small amounts) with up to 18 carbon atoms,

such as propylene, t-butene; Isobutene and 1-pentene;
halogenated olefins, such as chloroprene,
Tetrafluoroethylene, chlorotrifluoroethylene,
Hexafluoropropylene; Vinyl aryls, such as styrene,
o-methoxystyrene, p-methoxystyrene,
m-methoxystyrene, o-nitrostyrene, p-nitrostyrene,
o-methylstyrene, p-methylstyrene, m-methylstyrene,
p-phenylstyrene, o-phenylstyrene, m-phenylstyrene,
Vinyl naphthalene, vinyl and vinylidene halides,
such as vinyl chloride, vinyl fluoride, vinylidene chloride,
Vinylidene fluoride, vinylidene bromide, vinyl esters, such as
Vinyl formate, vinyl acetate, vinyl propionate,
Vinyl butyrate, vinyl chloroacetate,
Vinyl chloropropionate, vinyl benzoate,
Vinyl chlorobenzoate and the like; Acrylic and
Λ- alkyl acrylic acids, their alkyl esters, amides and
Nitriles, such as acrylic acid, chloroacrylic acid,
Methacrylic acid, ethacrylic acid methacrylate,
Ethyl acrylate, butyl acrylate, n-octyl acrylate,
2-ethylhexyl acrylate, n-decyl acrylate,
Methyl methacrylate, butyl methacrylate,
Methyl ethacrylate, ethyl ethacrylate, acrylamide,
N-methylacrylamide, N ₁ N - dimelhylacrylamide,
Methacrylamide, N-methyl methacrylamide,
N, N - dimethyl methacrylamide, acrylonitrile,
Chloroacrylonitrile, methacrylonitrile, ethacrylonitrile,
Maleic and fumaric acid and their anhydrides
and alkyl esters, such as maleic anhydride,
Dimethyl maleate, diethyl maleate, vinyl alkyl ethers
and ketones, such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether. ^ - chloroethyl vinyl ether,
Methyl vinyl ketone, ethyl vinyl ketone,
isobutyl vinyl ketone and butadiene, isoprene,
Cyclopentadiene, hexadiene-1,6, norbornadiene,
Dicyclopentadiene and the like; also pyridine,
N-vinylcarbazole, N-vinylpyrrolidine, acrolein,
Vinyl alcohol, vinyl acetal, vinyl butyral.
Other monomers that can also be copolymerized with ethylene are, for. B. carbon monoxide and formaldehyde; however, these are generally not preferred.

These copolymer resins should contain a larger amount of polymerized ethylene units. The copolymer preferably consists of about up to about 99% by weight of polymerized ethylene monomer, in particular from about 80 to about 99 wt .-% polymerized ethylene monomer, the exact Amount of the copolymerizable monomer chosen and the intended use of the invention Ethylenpolymerisatpräparaies depends.

Other suitable polymers are, for. B. Ethylene / Ethylidene norbornene / propene-1 terpolymers and Ethylene / hexadiene / propene-1-Tel polymers. Also in These terpolymers are dominated by the ethylene component and are available in amounts from about 50 to about 99% by weight present. The propene-1 is present in concentrations of from about 1 to about 50% by weight, and the remainder of the terpolymer consists of the third

ίο component.

Preferred base resins are the ethylene homopolymers, and preferred interpolymer base resins are, for example, ethylene-vinyl acetate; Ethylene-ethyl acrylate or its partially hydrolyzed ionic

Salts; Ethylene-acrylic acid or its ionic salts;

Ethylene-propylene or ethylene-styrene. A preferred one

Terpolymer is ethylene / propylene / ethylidene norbor-

nen.

The base resin is the main component of the ethylene polymer preparation and is usually in present at a concentration of from about 70% to about 99% by weight; the rest of the preparation is made from the remaining additives. A concentration of the base resin of about 90% by weight is preferred up to about 99% by weight, based on the total weight of the ethylene polymer preparation.

The exact concentration of each additive depends on various factors, e.g. B. of the desired rate of degradation, the molecular weight of the additive, the relative effectiveness of the additive, the desired physical properties of the ethylene polymer preparation according to the invention and the like.
The self-oxidizing additive can either be a polymer or an organic compound of low molecular weight, the majority of the units or the organic compound having at least one hydrogen atom bonded to a carbon atom, the tendency of which is greater than that of a hydrogen atom to self-oxidize is attached to a normal secondary carbon atom. So shows z. B. the polymer used as a self-oxidizing agent has a stronger tendency to self-oxidize than an unbranched polyethylene.

Polypropylene, which has hydrogen atoms bonded to tertiary carbon atoms, which are lighter are more oxidizable than the hydrogen atoms associated with normal secondary carbon atoms Polyethylene is a suitable self-oxidizing additive in polymer form. Examples for others self-oxidizing hydrogen atoms bonded to carbon atoms are the hydrogen atoms z. B. in allyl groups, benzyl groups, tertiary aliphatic groups, aldehyde groups, a-oxyhydrocarbyl or «-Halogenhydrocarbyl groups are present.

The Λ-olefin polymers which are produced at room temperature are also to be regarded as self-oxidizing polymers usually solid and following unit

(> o include:

-CH-CH ₂

(> 5 in the R for an alkyl group with about 1 to 18 Carbon atoms. Examples of such -olefin polymers are polypropylene, polybutene-1, polypentene-1, poly-4-methylpentene-1, polyhexene-1, polyoctene-1

and polyoctadecene-1. Preferably the ratio is from secondary carbon atoms to tertiary carbon atoms in the repeating unit of the self-oxidizing oc-olefin polymer between 1: 1 and 1: 16, especially between 1: 1 and 1: 6. Other suitable self-oxidizing additives are the polyalkylene oxides such as polyethylene oxide, polypropylene oxide, including the block polymers and random copolymers of these compounds and the like; polyunsaturated hydrocarbons such as polyterpenes.

The preferred self-oxidizing additive is atactic or isotactic, crystalline or amorphous Polypropylene. When used in the ethylene polymer preparations according to the invention, this provides Polypropylene a product that has the physical properties desired for its use and also shows fine cracking on the surface more quickly and disintegrates into small particles. as well suitable polymers are the block polymers, which for the most part consist of propylene blocks.

Suitable self-oxidizing organic compounds with a low molecular weight are the compounds whose molecular weight is less than about 5000, e.g. B. the derivatives of aliphatic and cycloaliphatic compounds with one or more allyl hydrogen atoms, such as myrcene, ocimene, Limonene (dipentene), cyclohexadiene, dicyclopentadiene, decahydronaphthalene, indene, tetrahydroindiene or Ethylidene norbornene; the unsaturated fatty acids such as elaostearic acid, linolenic acid, linoleic acid, oleic acid, Crotonic acid and sorbic acid, as well as the adducts of these and other unsaturated aliphatic and alicyclic Connections with z. B. maleic acid, acrylic acid or acrolein; Compounds with highly reactive Benzyl hydrogen atoms such as cumene and p-isopropylbenzoic acid.

The self-oxidizing polymers or compounds are preferably of low molecular weight Hydrocarbons. The presence of functional groups is not excluded, but it will also not considered essential.

The self-oxidizing additives are in concentrations from 0.01% by weight to 40% by weight, based on the total weight of the ethylene polymer preparation, present. A concentration of the self-oxidizing additive of 0.05 to 20 is preferred % By weight, in particular from about 0.1 to about 10% by weight, each based on the total weight of the Ethylene polymer preparations.

Any organic or inorganic metal salt is used as a further additive, at least one metal in question being a polyvalent transition part, preferably an organic salt of a polyvalent transition metal and in particular an organic salt of a polyvalent transition metal in which the electron transition is in the 3d or 4f- Secondary shell takes place. The transition metals are defined in the Periodic Table on the last page of the Handbook of Chemistry and Physics, The Chemical Rubber Co., 49th Edition (1968-65).

These are the elements of the 4th pearlode with atomic numbers from 21 to 30, the 3rd period with atomic numbers from 39 to 48 and the 6th pearlode with atomic numbers from 97 to 71. As transition metals in which the electron transfer takes place in the 3d secondary shell , V, Cr, Mn, Pe, Co, Ni, Cu, Zn, Zr and Ag from the 4th and 3rd pearls should be mentioned; Transition metals, in which the electron transition takes place in the 4f secondary shell, are e.g. B. Ce or Pr from the 6th period.

Inorganic salts of polyvalent transition metals suitable according to the invention are, for. B. ferric chloride, Zinc chloride, mercury chloride, chromium trichloride, Copper nitrate, copper sulfate, cobalt chloride, nickel sulfate, iron sulfate, iron bromide, zinc sulfate and mercury (II) sulfate.

Typical organic salts are the octoate, naphthenate, Acetate, stearate, or acetylacetonoate metal salts; however, other organic groups can also be used be used.

Examples of suitable organic salts of polyvalent transition metals are:

ι S cobalt acetate, cobalt octoate, cobalt naphthenate,
Iron naphthenate, iron octoate, lead stearate,
Lead octoate, zirconium stearate, cesium octoate,
Manganese (II) stearate, manganese (II) oleate,
Manganese (II) dodecylacetoacetate,
Cobalt acetylacetonate, cobalt (II) acetate,
Cobalt (II) oleate, cobalt (l I) stearate,
Cobalt OIJ-dodecylacetoacetate, copper (U) stearate, copper (II) oleate, iron (UI) acetate, zinc octoate,
Zinc naphthenate, iron distearate,
Potassium permanganate,

Potassium trioxalato cobaltate (III),
Trisethylenediamine cobalt (III) chloride,
Sodium hexanitrocobaltate (I! L) and
Potassium hexacyan cobaltate (III).

jo According to the invention, the polyvalent transition metal salts can be used individually or in combination. It has been found that certain combinations of polyvalent transition metal salts cause the preparation to break down more rapidly than a corresponding amount of the individual salts thereof Combinations; this applies in particular to mixtures of iron and cobalt salts.

The polyvalent transition metal salts are usually in amounts of about 0.002 wt .-% to about 2.0 wt .-% metal, based on the total weight of the Preparation, present. A concentration of about 0.005% by weight to about 1.0% by weight is preferred, in particular from about 0.01% by weight to about 0.1% by weight, based on the total weight of the preparation. That only such small amounts of polyvalent transition metal salts to achieve the weathering properties are required, is a particular advantage of the method according to the invention, because so Small amounts of salts usually affect the mechanical properties of the base resin not unfavorable.

Suitable oxidizing agents for the preparations according to the invention are all agents previously known for ethylene polymers, such as, for example, sterically hindered phenols, arylamines, thioureas, thiocarbamates, thioether esters, mixtures of these compounds or their adducts.

Under the designation "sterically hindered phenol" is a substituted or unsubstituted compound f, o to understand the at least one sterically handicapped person Group of the following structural formula contains:

HO-

709829/41

^{; c} 936f

wherein X is hydrogen, an alkyl group having 1 to about 10 carbon atoms, or a substituted or unsubstituted phenyl group and X ^{1 is} an alkyl group having 1 to about 10 carbon atoms or a substituted or unsubstituted phenyl group; this sterically hindered group tends to donate protons. In general, a sterically hindered phenol is chosen that does not volatilize or noticeably decompose at temperatures below about 200 °.

Examples of suitable phenol antioxidants are

Tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-

4'-hydroxyphepylpropionate] methane,

Stearyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxy- <

phenyl) propionate,

Distearyl-3,5-di-tert-butyl-4-hydroxy-

benzyl phosphite,

l, l, 3-tris- (5'-tert-butyl-4'-hydroxy-

2'-methylphenyl) butane (TOPANOL CA),

4-methyl-1,6-di- (2'-hydroxy-3'-tert-butyl-

5'-methylbenzyl) phenol,

2,4-di- (3 ', 5'-di-tert-butyl-4'-hydroxy-

phenoxy) -triazine,

2,2'-thio-bis (4'-methyl-6'-tert-butylphenol),

4,4'-thio-bis (3-methyl-6-tert-butylphenol),

3,5-di-tert-butyl-4-hydroxyanisole,

2,6-di-tert-butyl-p-cresol.

Suitable amine antioxidants are, for. B.N- Phenyl- / f-naphthylamine, N, N'-diphenyl-p-phenylenediamine,

p-isopropoxydiphenylamine,

N, N'-di- / 3-naphthyl-p-phenylenediamine, N, N'-di- (2-octyl) -p-phenylenediamine, N, N'-Di-3- (5-methylheptyl) -p-phenylenediamine, Aldol-a-naphthylamine.

4,4'-dioctyldiphenylamine,

4-octyldiphenylamine,

4-tert-butoxydiphenylamine and that

Polymer of

1,2-dihydro-2,2,4-trimethylquinoline.

Suitable thioureas are the polyalkylthioureas with up to about 4 carbon atoms in the Alkyl group such as trimethyl thiourea, 1,3-diethyl thiourea or ethylene thiourea. As thiocarbamates, their alkali salts, such as. B. Sodium dibutyl dithiocarbamate and the like can be used. Examples of thioether esters are dilauryl thiodipropionate and distearyl thiodipropionate. Suitable phosphites are e.g. B. the mono-, di- and trinonylphonylphosphites, distearylpentaerythritol diphosphite and the adduct of trinonylphenylphosphates with t, U-Trls- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane.

Further suitable antioxidants are dibutyl-p-cresol, p-cresol-formaldehyde resins, p-tert-alkylphenol-formaldehyde resins mixed with aminodethio formlates, aliphatic polyepoxides, organic phosphites, thiophosphates or di-thiophosphites; p-tert-Al-kylphenolformaldehyde resins In a mixture with mercapto compounds, 2-thione-2-mercaptodloxaphosphorinane compounds, tetraphenylsuccinic acid dinitrile or Triphenylmethane, or di-thiophosphate metal salts and mixtures of these compounds; aside from that Chelling agents, such as. B. carboxylic acids such as malonic acid, succinic acid, substituted oxamides, such as Oxanes, amino acids such as olycin and the like; Aminopoly

carboxylic acids, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediamine triacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, diaminocyclohexanetetraacetic acid, Diaminoethyl ether tetraacetic acid, ethylenediamine di- (o-hydroxyphenyl acetic acid); N-phenyl-N '- (p-toluenesulfonyl) -p-phenylenediamine, Ν, Ν-disalicylidene propylenediamine and the like; Pentaerythritol, sorbitol, resorcinol and other polyhydric alcohols and esters and mixtures of the compounds mentioned.

The antioxidant is used in such amounts that the preparation protects against oxidative degradation during its entire period of use is; an amount of 0.0025% by weight to 1% by weight, preferably 0.025% by weight to 0.1% by weight, is sufficient for this, based on the total weight of the ethylene polymer preparation.

Almost all ethylene polymers often contain small amounts of antioxidants; these However, amounts are generally not sufficient to add the ethylene polymer preparations according to the invention stabilize, and therefore additional amounts of oxidizing agents are usually required.

In certain embodiments of the present invention, however, no antioxidant is needed to be present, or it is only needed in very small quantities. In these cases, the ethylene polymer preparation becomes very quick under the influence of the outside world reduced. Such rapid degradation is not particularly important for the purposes in which a product is provided with a cover before it is used, which protects against the effects of sun, rain and Oxygen prevents. In use, the product is then removed from this coating, within used for a predetermined period of time and then thrown away to quickly get through the weather to be dismantled. Concentrations have proven to be useful for this embodiment of the present invention of the Oxidaiionsschutzmittel of only 0.0025 wt .-% proved to be satisfactory.

According to a further preferred embodiment of the invention, the use of certain antioxidants also brings further advantages. So are z. B. some anti-oxidants, such as thioureas, water-soluble. Products which are produced from the ethylene polymer preparations according to the invention and which contain thioureas can therefore be used for a long time in a relatively dry environment; conditions under humid outside world su, 1. B. under the action of rain or fog, the thioureas are leached, unil dus product decays more quickly. Biodegradable antioxidants can also be used, e.g. certain thio-ether esters such as dilauryl thiodipropionate and the like. Another possibility is the use of volatile antioxidants (such as mercaptomaleic acid or certain urea derivatives such as U-diethylurea. Due to its volatility, such an antioxidant is generally applied to the finished plastic product, e.g. by immersing the product In an α * solution of the antioxidant, by applicator with a roller or a spray device or the like. Volatile antioxidants can also be used together with less volatile agents, which are then smaller

Amounts present in the ethylene polymer preparation can be used. The volatile antioxidants volatilize under external conditions, and the plastic product can be more easily degraded. After all, you can also use one heat-resistant, but light-sensitive antioxidants are worked, z. B. with a-phenylindole or diphenylthiourea. A plastic product that contains these antioxidants can be used in the dark stored, but begins to degrade rapidly under exposure to sunlight.

It was also found that a previously irradiated ethylene polymer preparation was significantly higher Shows disintegration rates as a non-irradiated ethylene polymer preparation. As already mentioned, the preparation can also contain an antioxidant to ensure its stability before Improve irradiation.

In general, an ionizing radiation of about 1 to about 20 is used to accelerate the degradation Megareps, rep = physical X-ray equivalent (MGRPS) required, depending on the desired rate of disintegration it is also possible to work with higher or lower radiation doses. As radiation sources are suitable e.g. B. a Van-de-Graaff accelerator, cobalt GO or the like. All known radiation devices can be used be used, e.g. B. UV lamps, sunlamps, eddy flow plasma arcs, mercury lamps and the like

Such irradiation is particularly suitable for large plastic destruction plants, where they are used as waste occurring plastics are irradiated in order to reduce their rate of disintegration under external influences to enhance.

The manufacturing and analytical procedures described below were used in the following examples applied. There were two methods of destruction. In the first and mainly used The process was carried out with a two-roll mill (hereinafter referred to as "rolling process"), in the second method with a Banbury mixer (hereinafter referred to as "mixing method").

A two-roller mill 15 × 30 cm in size, ^{heated to 190 °} C. by a full supply of steam, which was heated for at least 15 minutes, was used. The opening between the rollers was kept as small as possible while the ethylene base polymer was being added, and then opened within about 1 minute after the ethylene polymer began to melt. Polypropylene or other self-oxidizing agents were added, followed by the oxidizing agent and any further fillers desired. The polyvalent transition metal salt was then slowly added over about 30 seconds. The material was processed for 2 minutes until it was homogeneous, then peeled off the rollers and cut into squares about 3 × 5 cm. It is pointed out that all known additives, such as pigments, lubricants, anti-caking agents, etc., can also be used. Unless otherwise stated, this rolling process was used in the examples.

In the mixing method, an about 2.2 kg drum forming Banbury Mlscher was used which was heated by steam supply to full Oehäuse and rotor for 5 minutes up to 19O ⁰ C. Then the ethylene base polymer and a self-oxidizing agent, such as. B. Polypropylene, Put in the mixer.

The plunger was moved down at full pressure of 5.6 kg / cm ² and the mixer operated at maximum forward speed for 3 minutes or until the material melted. Antioxidants, any fillers used, and polyvalent transition metal salt were added while the pressure was reduced to 0.7 kg / cm ² and the mixer was operated at the slowest forward speed for 1 minute. Then the stamp printing was done again

ίο increased to 5.6 kg / cm ² and the mixer operated at full forward speed for 2 minutes. The housing and rotors were then cooled with water, again working at the slowest forward speed. The material was then removed, made into plates and cut into pieces.

The samples made by the mixing or rolling process were compression deformed in the following way: A shape that was lined with a Mylar sheet,

was charged with the ethylene polymer preparation. The preparation was placed between preheated plates (190 °) placed, 4 minutes under low pressure (about 910 kg on the 38.7 cm stick), then 2 minutes under full pressure Pressure (about 2910 kg on the 38.7 cm stamp) set.

The plates were then cooled with water and the samples removed.

example 1

Ethylene polymer preparations were made in the manner described above manufactured, the low-density polyethylene (LDPE; density 0.922), polypropylene (PP; 98% isotactic material) as a polymeric self-oxidizing additive in amounts of 0% (control A), 0.1%, 0.3%, 2%. 5%, 10%, 20% and 30% and 0.10%

.15 Cobalt metal (Co) in the form of a cobalt naphthenal solution in petroleum ether, i.e. ligroin = "mineral spirits" in each case. There was also a control sample (Control B), which consisted of the base resin and the same amount of petroleum ether as described above as

• | o solution was added; another control sample (Control C) consisted of the base resin and 10% polypropylene. All of the samples described above were to 0.5 mm thick plates (or panels = "plaques") processed and in the manner described above weathered.

In the following table 1, part A and part B, the exposure times are given, which are until the point of becoming brittle ("break.") Until a carbonyl surface layer is obtained with a /? - value of

s »more than 1.7 (» FMIR R> 1.7 «) and until the extreme elongation has dropped below 20% (» 2 20% elongation «). The effect of the polypropylene in Control C on the acceleration of breakage is evident in a reduced activation time

S3 versus control B, which was not made of polypropylene Contains the cobalt salt In control A, the necessary blooming tent to become brittle should be compared to controls B or without cobalt Decrease C. The combined according to the invention

Ao system is supposed to create an interaction that makes the Embrittlement promotes considerably more quickly than in the case of the control samples. However, this effect also depends on the polypropylene concentration decreases, i.e. the blooming time to becoming brittle decreases when the

f> i Polypropylcnkonzentratlon increases) In all cases, however, the invention Äthylenpolyme · risatpräparate rapid brittle than the controls A, B or C

; c

There were identical ethylene polymer preparations before the weathering treatment with a radiation dose irradiated by 5 megareps; these samples required fewer with increasing polypropylene concentration Exposure times until the onset of the fragility

Table I.

dens and brittle more quickly than those not exposed at polypropylene concentrations of 2% or more Samples from Part A of Table I. The exposure times for the irradiated preparations are given in Table I, Part B, summarized.

Ethylene polymer in% by weight Co Required Exposure time in hours S20% part B !•ME S20% elongation preparation PP Part A strain Fracture. «> 1.7 LDPE 0.10 Fracture. FMIR 20th 60-150 0-20 30th 0.10 R> 1.7 20th 20th 60-150 0-20 70 20th 0.10 60 60-150 60 20th 20th 0-20 80 10 0.10 20-60 60-150 100 20th 20-60 60 90 5 0.10 60 60 150 60-100 20-60 100 95 2 0.10 100 60 150 100-150 20-60 100 98 0.3 0.10 150 60 150 150-250 60-100 60 99.6 0.1 0.10 150-250 60 150 60-250 20-60 150 99.8 0 0 150 60-150 > 500 250 150 500 100 *) 0 0 250 60 500 1000 500 500 100 **) 10 > 1000 > 150 500 90 ***) 750 7500

*) Control Λ.

**) Control B, reveals the same amount of polymer as the other samples. ** ♦) Control C.

Example 2

Example 1 was repeated, but instead of cobalt naphthenate, different cobalt octoate Concentrations was used. The ethylene polymer preparations each contained 2% by weight of polypropylene. The results are summarized in Table II, Part A and Part B,

Table 11

Ethylon polymer crisis <l Co required Uinaction / .cit S 20% prlipnrul, Ί in hours strain Ll) IMi Fracture. I'M ME 2 K> 1.7 250 Part A 1 150-250 96 0.10 200-250 150 150 97 0.075 200 150 150 98 0.050 100-150 100-150 150 98 0.025 100-150 100-150 150 98 0.010 ISO 100-150 150 250 98 100-150 150 98 2 150 150-200 150 250 Great B 1 150-250 96 0.10 200-250 ISO 150 97 0.075 150-200 ISO ISO 98 0.050 100-150 60 ISO 98 0.025 100-150 60 150 98 0.010 60-100 60 60 150 98 100-150 ISO 98 100 60

Example 3

This example illustrates the use of polypropylene with different tacticity and different molecular weight.

Ethylene polymer preparations were made which contain 98% LDPE (density 0.922), 2% polypropylene and Contained 0.05% cobalt in the form of a cobalt naphthenate solution in pctrolether; as a polypropylene component became a 98% isotactic polypropylene, an atactic polypropylene or an isotactic polypropylene wax (relatively low molecular weight) produced by pyrolysis of the isotactic polymer tes received was used. These preparations were processed into 0.5 mm thick plaques and placed on weathered in the manner described above.

After an exposure time of 150 hours, all of these preparations were brittle, had a carbonyl V) surface layer greater than 1.7 and showed a extreme elongation of less than 20%.

Example 4 In this example, LDPE became more different

^ Density used.

Ethylene polymer preparations were made which contain 98% LDPB, 2% polypropylene (98% isotactic) as self-oxidizing polymeric additive and 0.025% to 0.073% cobalt In the form of a cobalt octoate · or

to Kobaitnaphthenatlösung in Pcirolälher contained; the LDPE base resin had a density of 0.919, 0.922, 0.924, 0.925 and 0.928, respectively. These preparations were made to 0.5 mm thick flakes or 0.05 mm thick films and processed in the manner described above

ft * weathered.

All preparations showed accelerated breakage and were after exposure from 100 to 200 Hours brittle.

Example 5

Ethylenpolymerisatprparate were made, the 98% LDPE, 2% polypropylene (98% isotactic) as self-oxidizing polymeric additive and 0.025% cobalt in the form of a cobalt naphthenate solution in Contained petroleum ether; as the base resin, one obtained by polymerization in a tubular reaction device obtained polyethylene with a density of 0.924 or a through polymerization in an autoclave with ι ο Stirring device obtained polyethylene having a density of 0.925 is used. These preparations were made to 0.5 mm thick plates processed and weathered in the manner described above.

Both samples showed a similar weathering behavior. They were after an exposure time of Brittle for 150 hours, had carbonyl surface layers greater than 1.7, and their outermost Elongation had dropped below 10%.

20th

Example 6

Ethylene polymer preparations were made, the LDPE (density 0.922) as the base resin, polypropylene (98% isotactic) in amounts of 0%, 2%, 5% or 10% and 0.10% cobalt in the form of a cobalt naphthenate solution contained in petroleum ether. In addition, a control sample, which consisted only of the base resin, manufactured. All preparations contained lubricants (oleamide), Antiblocking agent to prevent sticking (= silica) and anti-oxidant (2,6-di-tert-butyl-4-methylphenol) in the quantities known for commercially available LDPE. These preparations were extruded at 205 ° through a 2.5 cm NRM extruder (National ■ Rubber Machinery) and then passed through the extrusion press 5 more times. After every 0.5 mm thick plaques were produced by extrusion presses, and their physical properties were examined and weathered according to the method described above.

The elongation values of the individual preparations, including the control, showed that the repeated extrusion did not cause premature degradation in extensibility. The extensibility of all preparations corresponded to the behavior of the control sample before the weathering test. All samples that Containing polypropylene and cobalt salt showed accelerated internal brittleness on weathering from 60 to 250 hours. The control remained even after an exposure time of 500 hours flexible.

Example 7

Ethylene polymer preparations were made with LDPE as the base resin (density 0.922), 1.16% Polypropylene as a self-oxidizing additive (98% isotactic) and 0.05% cobalt in the form of one of the Contained the following salts: 1) solid cobalt acetate, 2) cobalt octoate solution in petroleum ether, 3) cobalt naphthofio natural solution in petroleum ether and 4) the cobalt salts of a mixture of branched-chain Cg and Cg acids in Petroleum ether (known as Kobalt-Nuxtra). These preparations became 0.5 mm thick The platelets are processed and, as described above, (15 weathered. The exposure times until it becomes brittle, until a carbonyl surface layer is reached of more than 1.7 and until the extreme elongation has dropped below 10% are required summarized in Part A of Table III. All forms of cobalt salt were effective and resulted in one accelerated embrittlement within 200 hours or less. The dispersed in petroleum ether Salts showed greater potency, and cobalt naphthenate was found to be the most effective salt for that Preparations containing 1.16% polypropylene.

Similar ethylene polymer preparations were made using polyethylene of one density as the base resin of 0.922 g / ccm, as a self-oxidizing additive 6.48% polypropylene and each 0.10% cobalt in the form of the cobalt salts mentioned above. The exposure times that were required for these preparations are summarized in Part B of Table IH. All cobalt salts were active and led to accelerated Brittle in 200 hours or less. The salts dispersed in petroleum ether showed the 6.48% polypropylene containing preparations were more effective. All octoate, naphthenate or mixed branched chain Ce and Ce acid cobalt salts resulted, in combination with the preferred amount of polypropylene from 1 to 6.5%, in one accelerated embrittlement of low density polyethylene.

Table III

Co-SaI? Required exposure time in hours FMlR S 20% Fracture. R> 1.7 strain Part A > 150 > 150 acetate 200 150 100-150 Octoat 150-200 100 100 Naphthenate 150 100 100-150 Nuxtra 150-200 part B > 150 > 150 acetate 200 150 60 Octoat 100 100 60-100 Naphlhenate 100 150 60-100 Nuxtra 150 Example 8

Ethylene polymer preparations were made that contain 98% LDPE (density 0.922) as the base resin, 2% Polypropylene (98% isotactic) as a self-oxidizing additive and 0.05% metal in the form of metal salt solutions from cobalt octoate, iron octoate, manganese octoate, cemaphthenate, zinc octoate, lead octoate, zirconium octoate and calcium octoate in petroleum ether. These preparations were pressed into platelets and applied to the weathered in the manner described above.

The exposure times that were required for these preparations to become brittle were one Carbonyl surface layer of more than 1.7 and a decrease in extensibility below 20% are to be achieved from Part A of Table IV. Part B of Table IV summarizes the results obtained in the same preparations were obtained if they were exposed to a radiation dose of 5 Megareps have been irradiated.

709B29 / W7

Tubelle IV

Table V

Required action line
in hours

Fracture.

FMIR
Ä> 1.7

£ 20%
strain

Part A

Co-Ocloat

Fe-Oc toat

Mn octoate

Ce naphthenate

Zn octoate

Pb octoate

Zr octoate

Ca octoate

part B

Cu octout

Fe octoate

Mn octoate

Ce naphthenate

Zn octoate

Pb octoate

Zr octoate

Ca octoate

60-150

150

150

100

150

150

250

250-500

500

500

150

150

150

150

250

250-500

500

500

Example 9

60
60
150

60

60

150

150-250

150

15O ⁺

60

150

150

150-250

150

250 '

Ethylene polymer preparations were made with LDPE (density 0.922) as the base resin and self-oxidizing Additive polypropylene (98% isotactic) in amounts of 2% or 5% and mixtures of 0.05% Cobalt in the form of a cobalt naphthenate solution in petroleum ether and 0.05% iron in the form of an iron octoate solution contained in petroleum ether. Both preparations were pressed into 0.5 mm thick plaques and placed on the weathered in the manner described above. Then control samples were made from the same LDPE (density 0.922) manufactured and extruded to 0.5 mm thick films. Other identical preparations that, however, instead of the mixed metal salt system of cobalt naphthenate and iron octoate, 0.10% cobalt in the form of a cobalt naphthenate solution contained in petroleum ether were also processed into 0.5 mm thick platelets and weathered. The exposure times required to break a carbonyl surface layer of more than 1.7 and a reduction in elongation below 20% are shown in Table V. specified. At both polypropylene concentrations (2% and 5%) the mixed metal salt system fed an accelerated embrittlement of the ethylene polymer preparation. The only made of LDPE base resin The existing control was still pliable and brittle even after an exposure time of 750 hours. Compared with similar preparations containing the same amount of polypropylene and the same amount of Containing metal, but only in the form of cobalt, the mixed metal salt systems led to shorter ones Exposure times until it becomes brittle or until the extensibility has dropped below 20%. The results suggest that using a mixture of cobalt and iron is more effective than using it from cobalt alone; however, they also show that cobalt alone also gives satisfactory results be achieved.

approach

control

LDPE,% 98 98 95 95 150 100-150 100 100 PP,%
Co,% 2
0.05 2
0.1 5
0.05 5
0.1 60 60 60 0
0 Fe,% 0.05 0 0.05 0 0 Required Exposure time in hours 150 60 100 Fracture. 60-100 > 750 FMIR 60 - R> 1.7 ^ 20% 60 -

strain

Example 10

A first ethylene polymer preparation made of 95% LDPE (density 0.928) as the base resin, 5% polypropylene

\ s pyien (98% isotactic) as a self-oxidizing additive and a mixture in petroleum ether of 0.05% cobalt as cobalt octoate and 0.05% iron as iron octoate as well as a second ethylene polymer preparation made of 98% LDPE (density 0.928), 2% polypropylene (98%

isotactic) and a mixture in petroleum ether of 0.025% cobalt octoate and 0.025% iron octoate. Both preparations contained 0.05% Irganox-1010 as an antioxidant and 0.15% as a lubricant Erucamide and 0.15% silicon oxide as an antiblocking agent.

VS The specimens became 0.5 mm thick plates pressed, extruded into 0.5 mm thick sheets and 0.05 mm thick films, and then according to the above method described weathered. After an exposure time of 60 hours, the carbonyl surface layer rose both samples, which had been processed into 0.5 mm thick platelets, rose steeply. After 100 Both samples had a carbonyl surface layer of 2.1 hours. The samples were after 100 Hours, and an extensibility of less than 10% was with the first preparation after 60 hours and found in the second preparation after 100 hours.

The samples processed into films were tested at intervals of 20 during the weathering tests Hours examined. After 40 to 60 hours of exposure, the carbonyl surface layer of both took off Samples increased significantly, and the first preparation showed a more rapid increase. An extensibility of less as 20% was found in the first sample after 60 hours and in the second sample after 80 hours. The first preparation began to become fragile after 80 hours and the second preparation after 100 hours Hours, and the first preparation showed clear cracks after an exposure time of 500 hours.

The samples made into a film developed a carbonyl surface layer of more slowly than 1.7 than the other samples. A /? Value greater than 1.7 became in the first preparation after 100 hours and in the second preparation only after 150 hours achieved. The film from the first preparation began to become brittle after 60 hours and the second Film on after 100 hours. After an exposure time of 500 hours, the two film drops had disintegrated.

and the foils started along the surface cracks to split.

Example 11

The preparations of Example 10 were tested as extruded films and sheets for their lubricity investigated by determining the coefficient of friction (COF) according to ASTM method D 1894. All ι ο Film and foil samples had kinetic COF values of 0.16 to 0.03, indicating high lubricity correspond. A control film made from the same LDPE (density 0.928), but without lubricants and anti-caking agents had a COF of 0.60 which is very little or no no gliding ability.

irradiated sample 4.4 minutes, for the unstabilized irradiated sample 0.15 minutes and for the irradiated sample Control samples 0.20 minutes and 0.05 minutes, respectively.

By adding stabilizers to the combination of polyethylene, polypropylene and cobalt salt you can the highly active systems, normally without stabilizers in the presence or absence of The effects of the weather become brittle through oxidation, are stabilized against becoming brittle. Subsequent irradiation of the samples can reduce the effectiveness of the stabilizers. After exposure, the samples were treated with or without using the weathering procedure described above brittle.

Example 14

Example 12

Samples of LDPE containing polypropylene in amounts of 0.3%, 2.5% and 10% and salts in petroleum ether of cobalt, iron, cerium and zinc or mixtures of these salts in amounts of 0.025%, 0.10%, 0, 05% and 0.075%, but prepared without antioxidants, showed signs of oxidation at room temperature in the absence of sunlight and without the use of a weatherometer, and became brittle after 1 month or more. Irradiation with sunlight, UV light or very intense visible light accelerated this fragility. Irrespective of whether the samples were processed into platelets, extruded films or foils, or whether they were stored in resin form or processed later, this embrittlement could be detected in the absence of radiation. With this embrittlement in the absence of radiation, an odor occurs which is due to the oxidation and suggests the presence of short-chain aldehydes and acids .

Example 13

An ethylene polymer made of 98% LDPE (density 0.922) as the base resin, 2% polypropylene (98% isotactic) as a self-oxidizing additive and 0.075% cobalt in the form of a cobalt octoate solution in Petroleum ether made. A second preparation was made which, in addition to the above ingredients contained a stabilizer system of 0.05% Topanol CA and 0.15% dilauryl thiodipropionate. The control samples consisted of (1) 2% polypropylene in the LDPE mentioned and (2) pure LDPE. All preparations were pressed into 0.5 mm thick plaques and weathered in the manner described above. Also were the described samples pressed into 0.25 mm thick platelets and the above-mentioned isothermal DSC induction time analysis subjected at 180 °. The stabilized preparations had an induction time of 14.1 Minutes at 180 °, while the non-stabilized preparations only have an induction time of 0.25 minutes 180 ° showed. The controls had an induction period of 0.40 minutes or 0.16 minutes at 180 °.

The above samples and control samples were irradiated with 5 megareps prior to analysis. The isothermal The DSC induction time for the stabilized Ethylenpolymerisaitpräparate from (1) was 90% LDPE (density 0.922) as the base resin, 10% polypropylene (98% isotakic) as a self-oxidizing additive and 0.10% cobalt in the form of a cobalt naphthenate solution in petroleum ether and (2) 98% of the above LDPE, 2% Polypropylene (98% isotactic) and 0.025% cobalt made in the above form, both with a stabilization system from (a) 0.05% of a primary hindered phenol antioxidant that is four sterically hindered Contained phenolic groups through fatty acid ester bonds to a central carbon atom were bound; (b) 0.05% dilauryl thiodipropionate (DLTDP); and (c) 0.05% distearyl pentaerythritol diphosphite (DSPD) included. In addition, control samples were made without this stabilization system.

All preparations were pressed into 0.5 mm thick plaques and pressed in the manner described above weathered. To determine the isothermal DSC induction time at 180 °, the samples were also closed 0.25 mm thick plates processed.

The exposure times required to achieve fragility, a carbonyl surface layer of more than 1.7 and a drop in the extreme elongation below 20% are shown in Part A of Table VI summarized. In addition, the isothermal DSC induction times are from Part A of Table VI 180 ° can be seen.

It was found that the stabilized samples were somewhat compared to the non-stabilized samples longer exposure times were required to achieve a drop in extensibility below 20%. the Presence of stabilizers in the second preparation shows a clear effect on this Properties (decrease in extensibility and increase in the carbonyl surface layer) without the onset to delay the fragility significantly. The isothermal DSC induction time values show that these samples are well stable without Weatherometer treatment and have considerable induction times exhibit at 180 °.

fio Furthermore, preparations were made that both of the above Samples completely match, irradiated with 5 megareps before the experiments. The in the individual test procedures The required exposure times and the induction times achieved are given in Part B of Table VI

f> 5 summarized. The irradiation decreases the Extensibility less than 20% faster. After the irradiation, the stabilized samples were with or without Weather conditions brittle.

Table VI

I ¹ P,% Co,%

ΛΟ,% DSPD,% Broth.

1-'MIK R> 1.7 £ 20% elongation DSC induction / eil

in minutes

Part A (without irradiation)

0.10
0.025

Controls;

10 0.10

2 0.025

0.05
0.05

0.05
0.05

0
0

150
150

150
150

150
150

Part B (irradiation 5 megareps)

10 0.10 0.05 0.05

2 0.025 0.05 0.05

Example 15

This example illustrates the use of mixtures of organic metal salts with or without Stabilizers.

An ethylene polymer preparation made of 95% LDPE as base resin, 5% polypropylene (98% isotactic) as a self-oxidizing additive and a mixture of 0.05% cobalt as cobalt octoate and 0.05% iron as iron octoate, each as a solution in petroleum ether, which also has a stabilizing system from 0.05% of a hindered phenol antioxidant, 0.15% of a thioester (dilauryl thiodipropionate) and 0.05% distearyl pentaerythritol diphosphite. In addition, the same preparation without a stabilization system and a control sample were used made of 5% polypropylene in 95% LDPE. The preparations became 0.5 mm thick plaques pressed and weathered according to the method described above. For determining the isothermal DSC induction times at 180 ° the samples were processed into 0.25 mm thick plaques.

Both the stabilized and the unstabilized platelets were after 60 hours of treatment brittle in the weatherometer. The control sample made from LDPE and polypropylene alone was only used after brittle after an exposure time of 500 hours. The DSC induction time at 180 ° was for the stabilized Sample 19.6 minutes and for the unstabilized sample 0.76 minutes; the control sample had a DSC induction time of 0.28 minutes.

Samples of the above preparations were irradiated prior to testing. Both the stabilized and even the non-stabilized sample was in the. within 60 hours after this irradiation Weatherometer brittle, while the brittle control had an exposure time of 250 hours needed. The DSC induction time at 180 ° for the irradiated stabilized sample was 1.4 minutes, for the ' irradiated unstabilized sample 0.11 minutes and for the irradiated control 0.20 minutes.

Example 16

This example explains the application of various Antioxidants in ethylene polymer preparations made from 95% LDPE (density 0.928) as the base resin,

150 150 24.8 150-250 150-250 26.7 150 60 0.10 150 150 0.14 150 60 0.12 150 60-100 0.13

5% polypropylene (98% isotactic) as a self-oxidizing additive and a mixture of 0.05% cobalt in the form of cobalt octoate and 0.05% iron in the form of iron octoate dissolved in petroleum ether. Any preparation contained 0.05% of one of the following sterically hindered phenol antioxidants: Irganox-1010, Santonox R, Topanol CA, Irganox-1076 or Ionol. There were Manufactured platelets with a thickness of 0.25 mm and measured the isothermal DSC induction time at 180 °. The DSC induction times of the preparations with the specified antioxidants were; 9.8 Minutes, 12.5 minutes, 6.2 minutes, 6.2 minutes and 3.5, respectively Minutes.

Example 17

This example illustrates the effect of secondary stabilizers with primary stabilizers in the presence a mixture of organic transition metal salts.

An ethylene polymer preparation was made, the base resin being 98% polyethylene (density 0.928) as self-oxidizing additive 2% polypropylene (98% isotactic), a mixture of 0.025% cobalt in Form of cobalt octoate and 0.025% iron in the form of iron octoate, each dissolved in petroleum ether, and as Anti-oxidant contained 0.05% Irganox-1010. A second preparation consisted of the same Components, but also contained 0.05% distearylpentaerythritol diphosphite. A third preparation corresponded to the second sample, but contained additional 0.15% dilauryl thiodipropionate. 0.25 mm thick plaques were produced from each preparation and at 180 ° examined for their isothermal DSC induction times. The DSC induction times were for first sample 7.9 minutes, for the second sample 10.0 minutes and for the third sample 15.0 minutes.

Example 18

An ethylene polymer preparation was made because :; made of 99% LDPE (density 0.928) as base resin, 1% Polypropylene (98% isotactic) as a self-oxidizing additive and 0.25% of a mixture of 0.0125% Cobalt in the form of cobalt octoate and 0.0125% iron in Form of iron octoate (0.025% mixture) as well as 0.05% of the hindered phenol antioxidant Irganox-1010 and 0.05% distearyl pentaerythritol diphosphite. Then a second preparation of 98%

Polyethylene, 2% polypropylene and 0.05% of the above organic metal salt mixture. A third The preparation consisted of 95% polyethylene, 5% polypropylene and 0.10% of the organic metal salt mixture. These preparations were pressed into 0.25 mm thick plaques and examined for their isothermal DSC induction times at 180 ° and 200 °. The samples were then aged in a compressed air oven at 43 ° for 1500 hours without any significant reduction in the isothermal DSC induction times occurred at 200 °. However, if they were irradiated with a UV lamp for 8 hours, the induction time decreased 180 ° by 99.5%, 99.0% or 86.0% and the induction time at 200 ° could no longer be measured; this shows that the Preparations irradiated with UV light lost their stability.

Example 19

There were similar Äthylenpolymerisatpräparate prepared as in Example 18, but 0.10% of the hindered phenol antioxidant and 0.10% distearylpentaerythritol diphosphite. the after 1500 hours showed an increased content of antioxidant platelets Aging at 43 ° the same stability behavior and after 8 hours of irradiation with UV light the same percentage loss of induction time at 180 ° like the preparations of Example 18.

Example 20

Test samples of the preparations of Example 18 were made with a Van de Graaff generator with 5 megareps irradiated. This exposure resulted in an 80-55% decrease in the isothermal DSC induction time 180 °.

Further samples of the preparations according to Example 18 were exposed to intense light from an argon vortex flow plasma arc, which was 30% below 4000 A, irradiated for 6 seconds; this led to a reduction the isothermal DSC induction time at 180 ° by 28 to 43%.

The samples of the preparations of Example 18 were exposed to UV light from a mercury lamp for 8 hours irradiated, the isothermal DSC induction time at 180 ° was reduced by 99.5 to 86%.

Example 21

There was prepared a Äthylenpolymerisatpräparat consisting of 98% LDPE (density 0.922) as a base resin, 2% Polypropylene (98% isotactic) as sclbstoxydicrendem additive, 0.05% cobalt in the form of cobalt octoate and 0.05% of the hindered phenol was Oxydationsschulzmittels . In the manner described above 0.25 mm thick test plaques were made and irradiated using a Van de Graaff accelerators with radiation doses of 0, ₁ J 2, 5, 7 and 10 Megareps. These samples were then examined for their induction times at 180 ° by isothermal DSC analysis and it was found that a radiation dose of 1, 2, 5 and 10 megareps is sufficient to compare the (10 isothermal DSC induction time at 180 ° of the non-irradiated sample by 55%, 73%, 84% and 99%, respectively.

Example 22 ,,,

This example illustrates the influence of an opacifying agent on the rate of embrittlement. An ethylene polymer preparation was prepared, the base resin 98% LDPE (density 0.922), as a self-oxidizing additive 2% polypropylene (98% isotactic table), 0.05% cobalt in the form of a Kobaltoctoatlösuni in petroleum ether, 0.05% of the hindered phenol -Oxyda tion protection agent Irganox-1010 contained. A second preparation contained the above ingredients and an additional 2% titanium dioxide. A control sample was then made from: 98% LDPE, 2% polypropylene and 2% titanium dioxide. These preparations were pressed into 0.5 mm thick plaques and weathered in the manner described above. The exposure times that were required until the onset of brittleness, to achieve a carbonyl surface layer of more than 1.7 and to sink the extensibility below 20% were 100 hours for the first preparation, IOC hours and 100 to 150 hours for the second preparation 150 hours, 100 hours and 150 hours The control showed none of these phenomena even after 250 hours under the same conditions.

Example 23

Three ethylene polymer preparations were made, each containing 98% LDPE (density 0.922) as Base resin, 2% polypropylene (98% isotactic) as a self-oxidizing additive, 0.10% cobalt in the form a cobalt octoate solution in petroleum ether and 0.05% of the hindered phenol antioxidant Irganox-1010 and also contained 2% titanium dioxide, zinc oxide and calcium carbonate as opacifiers. To the Three samples were made of 98% LDPE and 2% polypropylene with 2% each of the control named opacifiers passed. Then, platelets with a thickness of 0.5 mm were made from these preparations pressed and weathered in the manner described above. After 200 hours, the first three showed Specimen clear surface cracks and brittleness. The cracking was with the zinc oxide and titanium dioxide containing samples stronger. A carbonyl surface layer greater than 1.7 and a subsidence of the The samples containing titanium dioxide were stretchable below 20% after 150 hours or 150 to 220 hours Hours, for the samples containing zinc oxide after 100 to 150 hours or after 100 hours and for the Calcium carbonate-containing samples after 150 hours or 150 to 200 hours. The control samples did not show any of these phenomena even after an exposure time of 350 hours.

Example 24

Ethylenpolymcrisatpräparalc were made, the 98% LDPE (density 0.922) as the base resin, 2% polypropylene (98% isotactic) as a self-oxidizing additive, 0.05% cobalt in the form of a cobalt octoate solution in petroleum ether and 0.05% of a hindered phenol antioxidant Irganox-1010 as well as 0.05% distearylpentaerythrl diphosphite; 0.05% of one of the following pigments was added to each of these preparations. As a control, the same preparations were made without pigments. The specimens were then pressed into 0.5 mm thick plaques and weathered in the manner described above. After 130 hours, all samples, including the control, were very brittle and had elongation values below 20%. The presence of the colorants had no effect on the weathering behavior of the degradable preparations according to the invention .

7W BW / 417

• rr

IO

Example 25

Ethylene polymer preparations were made 98% LDPE (density 0.922) as the base resin, 2% polypropylene (98% isotactic) as the self-oxidizing one Additive and 0.05% metal in the form of solid cobalt naphthenate, cobalt octoate, cobalt stearate, cobalt acetylacetonate, iron distearate, copper stearate or Manganese stearate and 0.05% of the hindered phenol antioxidant contained. These preparations were pressed into 0.5 mm thick plaques and weathered in the manner described above. All samples showed a carbonyl surface layer of more than 1.7 after 150 hours and after 150 to 250 hours Fragility and reduced ductility.

Example 26

Ethylene polymer preparations were made that contain 98% LDPE (density 0.922) as the base resin, 2% Polypropylene (98% isotactic) as a self-oxidizing additive, 0.10% metal in the form of one of the following Metal salts and 0.05% of the phenol antioxidant Irganox-1010. When metal salts were Chromium trichloride, cobalt chloride, copper (II) acetate, copper (II) chloride, copper (II) oxalate, iron (II) chloride, Iron (U l) oxalate, lead acetate, manganese acetate, mercury (II) chloride, potassium permanganate, copper chloride and ammonium vanadate are used. The preparations were pressed into plaques with a thickness of 0.5 mm and weathered in the manner described above. All preparations were brittle after 500 hours; Preparations, which contained copper (II) acetate, iron (! I) chloride, manganese acetate and ammonium vanadate were already after Brittle for 250 to 350 hours.

Example 27A

Ethylene polymer preparations were made with a very dense polyethylene (density 0.962), as a self-oxidizing additive 0%, 1%, 2% and 5% polypropylene, which was 98% isotactic, and Contained 0.05% cobalt in the form of cobalt octoate. In addition, similar preparations were made to the made of polyethylene with a density of 0.958, made of 0%, 1%, 2% and 5% of this polypropylene and the same amount of cobalt octoate, respectively, as above. All of these preparations also contained 0.05% of the hindered phenol antioxidant. The preparations were too 0.5 mm thick plates processed and weathered in the manner described above, after a Exposure time of 60 hours were all brittle.

Example 27B

The same Äthylenpolymerisatpräparatc were prepared as in Example 27A, but containing iron octoate instead of cobalt octoate. All of these preparations were brittle after 20 to 60 hours.

Example 28

Ethylene polymer preparations were made that contain a very dense polyethylene (density 0.962) as the orundic resin, O ¹ Vb, 1%, 2% or 5% polypropylene (98% isotactic) and 0.05% metal in the form of a mixture as a self-oxidizing additive equal parts cobalt octoate and iron octoate contained as a solution in petroiather. In addition, similar preparations were made from polyethylene having a density of 0.958 and 0%, 1%, 2% and 5%, respectively, of the above polypropylene and 0.05% of the above metal salt solution. These preparations 0.05% of the hindered phenol antioxidant Irganox-1010 was added in each case. The preparations were pressed into 0.5 mm thick plaques and opened weathered in the manner described above. After 20 to 60 hours, all preparations containing propylene were gone brittle. The preparations that did not contain polypropylene, however, required a full 60 hours of exposure time until they were brittle.

Example 29

A. Three preparations made of 99% very dense polyethylene (density 0.962), 1% polypropylene (98% isotactic) and 0.05% metal in the form of (I)

Manganese (II) octoate, (2) zinc octoate and (3) a mixture of equal parts of these salts.

B. Preparations similar to those under A were made, but did not contain any polypropylene as a self-oxidizing additive.

C. There were three preparations made of 99% polyethylene with a density of 0.958, 1% polypropylene each as above and 0.05% of one of the above metal salts.

D. Similar preparations were made with Group C polyethylene but did not contain polypropylene.

E. Three preparations were made containing 99% polyethylene with a density of 0.960 (made by Mixing of 78% polyethylene with a density of 0.962

with 22% polyethylene with a density of 0.958), 1% polypropylene as above and 0.05% of one of the contained above metal salts.

All preparations in groups A to E also contained 0.05% of the sterically hindered phenol-oxy-

.15 antidation agent Irganox-1010. The to platelets Prepared preparations subjected to the weathering procedure were all brittle after 60 hours. The only exception was the preparation, the manganocloat in polyethylene with a density of 0.962

4c without polypropylene - this preparation was only brittle after 100 hours.

Example 30

Äihylenpolymcrisatpräparaic were made, the LDPE (density 0.922) as the base resin, polyethylene glycol with a molecular weight / between 6000 and 7500 in Amounts of 0.5% or 2.0% as self-oxidizing additive (PEO) and 0.05% cobalt in the form of a Contained cobalt tooate solution in petroleum ether. A first Control sample consisted only of LDPF., A second control sample of 2% PEO in LDPE and a third Control sample made from 0.05% cobalt In the form of a cobalt octoate solution in petroleum ether and LDPE. All these

Preparations were pressed into 03 mm thick plaques and weathered in the manner described above.

The exposure times that were required until the The carbonyl surface layer began to become fragile was more than 1.7 and the extreme elongation was below

Ao fell by 20%, are summarized in Table VIl, Part A. It is evident that by adding PEO to the second control sample, the exposure tented up to Breakage could be significantly reduced compared to the first control sample. Were also

t * 0.05% cobalt was added, the phenomena listed above occurred even more quickly. The resolution achieved by using a mixture of 2% PBO In LDPE plus the presence of 0.05% cobalt

brittleness is not as great as that Acceleration obtained by adding 0.05% cobalt to pure LDPE (third control sample). the Adding 0.5% PEO to LDPE in the presence of 0.05% cobalt resulted in all weathering phenomena, with the exception of embrittlement, at speeds higher than the addition of 0.05% Cobalt to LDPE (third control). A 2% concentration of the PEO in the LDPE / PEO blend surprisingly causes, in the presence of 0.05% cobalt, a relative slowing down of the degradation phenomena, while degradation is accelerated when the PEO concentration in the LDPE / PEO blend Is 0.5%.

The preparations and control samples described above were used in a further weathering test irradiated with a radiation dose of 5 megareps. The required exposure times are from Part B. can be seen in Table VII. Particularly good acceleration values are achieved through irradiation in the case of mixtures obtained from 0.5% PEO and 0.05% cobalt in LDPE. The required exposure times were shorter than for the non-irradiated sample and for the non-irradiated or irradiated third control sample.

Table VIl PEO,% Co,% Required exposure time in, hours 45 FMIR S 20% Surface cracks LDPE,% Fracture. R> 1, , 7 stretching 250 500 Part A 2 0.05 500 60 60-150 150 98 0.5 0.05 500 99.5 Controls: 0 0 > IOOO 100 2 0 750 150 150 500 98 0 0.05 250 100 150 250 250 part B 2 0.05 500 60 60 150 98 0.5 0.05 150 99.5 150 500 Controls: 0 0 1000 100 2 0 750 60 150 250 98 0 0.05 250 than at I.
the preparations with 2% acrylic silurehali. All 100 example 31

Ethylene polymer preparations were made which consisted of an ethylene-acrylic acid mixed polymer (EAA) with an acrylic acid content of 2% as the base resin and contained 0.05% cobalt in the form of one of the following salts: solid cobalt acetate , cobalt octoate solution in petroleum ether, cobalt naphthenate solution the cobalt salts of a mixture of branched Cb and d acids (Nuxtra). In addition, preparations were made from a BAA mixed polymer with an acrylic acid content of 7% and 0.10% cobalt in the form of the metal salts listed above. The preparations were pressed into 0.5 mm thick plates and weathered on the catfish described above. The action tents that were required until the preparations were brittle, the extensibility dropped below 20% and cracks became visible are listed in Part A of Table VIII. In the preparations with 2% acrylic acid content, all of the cobalt salts mentioned led to accelerated degradation. The preparations with an acrylic acid content of 7% became brittle less quickly, but the surface cracks appeared more quickly. The above-mentioned cobalt salts led to acceleration. system degradation of the preparations.

Ethylene polymer preparations were also made from the above-mentioned EAA mixed polymers which, however, only contains cobult acetate in cobalt concentrate metal ions of 1.0%, 0.1%, 0.05% and 0%. The preparation without cobalt salts as Control for all EAA mixed polymers. The required exposure times as well as the times without

ss weathering treatment that has elapsed until the samples become brittle are shown in Part B of Table VIII summarized.

The copolymers containing cobalt acetate and 2% acrylic acid were administered according to ISCstUndlger

Aor treatment brittle, whereby the cobalt concentration played no role, and were also without Weathering treatment brittle in less than 3 months. The preparations containing cobalt acetate and 7% acrylic acid were in less than 500 hours

The exposure time was brittle, showed within 150 Hours of Surface Cracks and Were Also Without Weathering Treatment In Less Than 6 Months brittle.

Table VIII
Part A

/ (ρ

AA *),% Co,%

Co-SaIz

Required exposure time in hours
Fracture. 20% elongation

Cracking

2 0.05 acetate 250 150 200 2 0.05 Octoat 100 100 200 2 0.05 Naphthenate 100 100 200 2 0.05 Nuxtra 150 100-150 200 7th 0.10 acetate > 250 150 7th 0.10 Octoat > 250 100 7th 0.10 Naphthenate > 25O 150 7th 0.10 Nuxtra > 25O 150

part B

AA *),% Co,% Co-SaIz Required Exposure time in hours Break.without Fracture. Creasing Vcrv.'itt treatment 2 1.0 acetate 150 250 S3 months 2 0.1 acetate 150 250 S3 months 2 0.05 acetate 150 200 S3 months 2 0 500 7th 1.0 acetate 500 100 S3 months 7th 0.1 acetate 250 150 4-6 months 7th 0.05 acetate 500 150 3-4 months 7th 0 500 *) Acrylic acid

Example 32

Preparation samples were produced which contained ethylene / vinylucctate mixed polymer resin (EVA) with a vinyl acetate content of 10%, 18%, 28% and 33% in combination with 0.10% cobalt in the form of cobalt toate solution in petroleum ether. Control samples of the above preparation without cobalt toate were then made. All preparations were _{pressed into 5ί} plates and weathered in the manner described above. After 200 hours, the preparations containing 10% vinyl acetate showed surface cracks and were brittle after 350 hours. The preparations containing 18% vinyl acetate showed surface giants after 230 hours and failed after 330 hours when they were bent without becoming brittle.

The preparations with 28% vinyl acetate content also showed a failure not caused by brittleness during bending after 230 hours. Such a failure without cracking is more likely to be attributed to a crack than to a break. The preparation, which contained 33% vinyl acetate, was postponed after 900 hours. All control samples were still pliable even after 500 hours and did not fail.

Example 33

Ethylcnpolymerisatprnpanite were produced which contained LDPE (density 0.922) as base material and 2% isotactic polypropylene as self-oxidizing additive as well as the transition materials and anti-oxidizing agents given in Table IX, amounts in percent by weight based on the total composition. The homogeneous preparations were then compression-molded into 0.25 mm thick platelets and examined for their thermal stability at 200 ° by means of the DSC induction process. All preparations were subjected to a weathering treatment in an Atlas XW Weatheromoter ι after 130 hours they were all brittle and showed an extreme elongation of less than 20%. The unmodified polyethylene had an original elongation value of about 400% and this had not changed noticeably even after 130 hours. The values and results are summarized in Table IX.

Table IX

Ansal /

u h c

hi j k 1 m η ο

Transition metal

Cobalt *),% 0.05 <-

Hiscn **),%

- »0.025 <0.025« - - 0.05 <-

-> 0.05

Oxyclationsscluilzmittcl, %

Λ
B.
C.
I)

DSC 'induction
at 200 C

Minutes

0.05 <-

0.075 -

0.075 0.1

0.075 - - - 0.1 - - 0.075 -

0.075 - - - 0.075 - - 0.075 0.1 - - - 0.1 - - 0.1

5.8 8.2 13.5 19.6 2.5 3 7.5 4.6 0.05 1.5 1.5

0.08 0.8 0.1

*) 12 "/ ,, coballocal solution in Pctroläthcr.

**) 50:50 mixture of 12 "A cobalt octoate and 9% l-jsen-nuxtra in pelrolite. Λ 'Ictrakis- | mclhylcn-.V (3', 5'-di-lcrl.-hutyl4'-hydroxyphcnyl) propionate] -mcthan. ! 5 Dislcarylpcnlacrythritol diphosphil.

C Aildukl von Tri- (nonylphcnyl) -phosphil and!,!, S-Tri-IS-lcrl.-hutyM-hydroxyl ^ -methylphcnyD-bulan. D Mixture of pentaerythritol and the thiodipropional ester of l, l,.} - tris (V-tert-bulyl-4'-hydroxy-2'-methylphenyl) -hutane.

Example 34

Two batches were made from the components of Example 33, which were then combined mixed and processed into degradable ethylene polymer preparations, which have the same chemical Composition had the same as batches a to ο of Table IX.

The first basic approach consisted of LDPE, 2% isotactic polypropylene and 0.005% of the antioxidant A.

The second basic approach contained LDPE, 2% transition metal in the forms mentioned in Example 33 and the antioxidants B, C and D in such amounts that after mixing the two basic approaches The finished preparation obtained had the desired concentration of antioxidants.

The degradable ethylene polymer preparations were made by running on a two-roll mill Processed 97.5 parts of the first basic approach with 2.5 parts of the second basic approach. From the homogeneous Preparations were then made by compression molding 0.25 mm thick plaques. These were after 150 hours of weathering treatment brittle and had an ultimate extensibility of less than 20%. The DSC induction times determined at 200 ° for the individual preparations are listed below:

Ansal /. Minutes Ansal /. Minutes a 9.6 G 3.0 b 13.6 H 9.8 C. 13.3 i 0.05 d 18.9 j 0.15 π 3.0 k 1.0

The second approach per se had a DSC induction time greater than 60 prior to mixing Minutes.

Example 35

In this example the degradable ethylene polymer preparations were made made by mixing three different basic approaches together. The same components as in Example 33 were used used, and the finished preparations had the same chemical composition as the approaches * a to ο of example 33.

The first basic approach consisted of LDPE, 20% isotactic polypropylene and 0.05% of the antioxidant A.

The second basic batch contained LDPE, 2% of the transition metal salts of Example 33 and the antioxidants B, C and D in such amounts that the finished preparation after mixing the three basic approaches contained the desired concentrations of antioxidants.

The third basic approach consisted only of LDPE.
The degradable ethylene polymer preparations were obtained by processing 9.75 parts of the first basic batch, 2.5 parts of the (, 0 second basic batch and 87.75 parts of the third basic batch on a two-roll mill. The homogeneous preparations then became 0.25 mm strong platelets were compression deformed. These were all brittle within 150 hours during the weathering treatment and showed an extensibility of less than 20%. The DSC induction times determined at 200 ° for the individual preparations are summarized below:

Ansal / Minutes approach Minutes U 8.5 G 3.8 b 14.0 H 8th C. 11.7 i 0.05 d 19th j 0.1 e 2.9 k 1.1

The second basic approach per se possessed before Mix with a DSC induction time greater than 60 minutes.

Example 36

A number of approaches were made that included transition metal and antioxidants. Cobalt in the form of a cobalt naphthenate solution in petroleum ether served as the transition metal. Then degradable ÄthyJenpolymerisatpräparate were prepared by the base stock were processed together in a two roll mill 95.5 parts of LDPE (density 0.922), 2 parts of polypropylene and 2.5 parts. The preparations obtained in this way were processed into 0.25 mm thick plaques by compression molding, and their DSC induction times were then determined in minutes at different temperatures. The values and results are given below:

(irunilunsut / 2 3 4th I. 96.8 97.0 97% Polyethylene 96.0 2.0 2.0 2.0 cobalt 2.0 (as metal ber.) 1.0 1.0 0.04 Oxidation protection 2.0 medium A (Table IX) DSC induction time of the preparations in Minutes: 0.1-1.3 0.1 0.1 at 200 ^° C 11.5 0.25-3.6 0.2 0.27 at 180 ^° C 6.4 0.15 - at 17O ⁰ C - _ 0.2 at 160 ^° C -

35

45

Before blending with more polyethylene and polypropylene, batches 1, 2, and 3 owned 200 "a DSC induction time of more than 60 minutes and the basic batch 4 a DSC induction time of 37 minutes. The values show that the basic batches are considerably more stable than those made from them degradable preparations, although they have a higher metal content.

Example 37
Part 1

A first basic approach was made, which (> above) LDPE (density 0.922), 2.05% polypropylene and 0.005% Oxyda'.ionschutzmittel A (Table! X).

Then a second basic approach made of LDPE, 2% cobalt in the form of a cobalt octoate solution in petroleum ether, 2% antioxidant A (Table IX) and (> 5 4% Antioxidant D (Table IX) was prepared.

An ethylene polymer preparation was obtained by adding 97.5 parts of the first basic batch dry 2 5 parts of the second basic approach were misused. This dry-mixed preparation showed no degradation on storage.

Part 2

A third basic approach was made, that of LDPE 205% polypropylene as a self-oxidizing one Additive and 0.05% antioxidant A (Table IX).

An ethylene polymer preparation was obtained by adding 87.75 parts of LDPE in dry form. 975 Mixing parts of the third approach and 2.5 parts of the second approach from Part I together This dry-mixed preparation showed no signs of degradation during storage.

part 3

It became a dry blend of 95.5 parts of the LDPE base resin, 2.5 parts of the second base batch and 2 parts of polypropylene as a self-oxidizing additive. This preparation was at the Storage stable.

Example 38
part One

The dry-mixed, degradable ethylene polymer preparation according to Part 1 of Example 37 was on hot extruded on a 2.5 cm extruder into a uniform sheet 0.5 mm to 0.75 mm thick. A portion of this film was then compression-molded into 0.25 mm thick plaques; these possessed accordingly the DSC induction time method a thermal stability of 25.9 minutes at 200 °. Another part of the slide was processed on a hot two-roll mill and then compression-molded into 0.25 mm thick plaques, which had an induction time of 28.3 minutes.

Part 2

The dry-mixed degradable ethylene polymer preparation from Part 2 of Example 37 was the above subject to the procedures described in Part 1 of this example. The DSC induction times of the compression set Platelets were 26.9 minutes and 23.0 minutes, respectively.

part 3

It was a degradable ethylene polymer preparation prepared by 95.5% of the in dry form LDPE base resin with 2% of the polypropylene used as a self-oxidizing additive and 2.5% of the second basic approach from Part 1 of Example 37 were mixed. This dry mixed preparation was then hot on a 2.5 cm extruder to a uniform looking 0.5 mm to 0.75 mm thick Extruded film. This film was then used in the manner described in Part 1 of this example Compression deformation made of platelets; these had DSC induction times of 22.0 minutes and 19.6, respectively Minutes.

Example 39
Part!

Mixtures of cobalt octoate as a solution in petroleum ether and the corresponding amounts of antioxidants were applied to finely divided silica

applied, whereby free flowing dry powders were obtained which could then be used to produce more degradable Ethylene polymer preparations were used. Three degradable preparations have been made by the components listed below were processed on a two-roll mill and then added 0.25 mm thick platelets deformed by compression. The composition of the preparations and their induction times 200 ° are summarized below:

preparation 2 3 1 97.2 97.2 LDPE (density 0.922),% 97.3 2 2 Polypropylene,% 2 0.05 0.05 Cobalt,% 0.05 (as metal ber.) Oxidation protection / medium (see table IX) 0.05 0.05 A. 0.05 0.075 - B. - - 0.075 C. - 13.5 18.1 DSC induction / cil, 17.1 Minutes

Part 2

Three other degradable preparations were made in the manner described above, but with the Anti-oxidant added immediately and only the cobalt octoate on the finely divided silica was applied. These preparations had DSC induction times of 5.8 minutes, 8.2 minutes and 14.2, respectively Minutes.

All preparations of Example 39 were brittle after 150 hours of weathering and showed a extreme elongation of less than 20%. In contrast, that was used as the starting material Polyethylene was not brittle and was extensible both before and after the weathering treatment of more than 400% under the same conditions.

Example 40

In order to determine the degradability of the ethylene polymer preparations on storage, two Prepared preparations. The first preparation was obtained by turning all the components hot into one homogeneous product were processed. The second preparation was made by separating two Basic approaches, one of which contained the self-oxidizing polypropylene and the other the metal salt, dry mixed together. The degradable preparations thus obtained had the same chemical Composition and were just made in different ways.

Part

A first basic batch was made of 78.76 parts of polyethylene, 0.2 part of erucamide, 1.0 part Silica, 10 parts polypropylene, 0.02 part each of antioxidants A and B (Table IX) and contained 10 parts of a leather yellow dye concentrate in polyethylene; these components were on processed in a roller mill and then granulated.

A second basic approach was made from 97.68 parts of polyethylene, 0.06 parts each of the antioxidants A and B and 2.2 parts of cobalt stearate also produced on a roller mill and processed into grains.

Then there were equal amounts of these two basic approaches dry mixed in a high speed laboratory mixer.

Part 2

A degradable preparation was made by placing it on a roller mill in the shape of a hot

ίο melt 88.22 parts of the same polyethylene, 0.1 part Erucamide, 0.5 part of silicon oxide, 0.04 part each of antioxidants A and B, 5 parts of polypropylene, 1.1 parts of cobalt stearate and 5 parts of the leathery yellow color concentrate mixed together and the uniform Mixture processed into grains.

Since the beginning of the degradation can be recognized by a sharp increase in the melt index, this property became exploited to determine whether degradation has occurred or not. The granular materials

were stored in air at 80 "and were in Samples are taken for melt index measurements at certain intervals. It has been found that according to Part 2 produced grains between the fourth and sixth week a steep increase in the melt

2s showed xes and also developed an odor, while the grains according to Part 1 show neither an increase in melting inciex nor an odor development let determine. The results are summarized below:

Melt index, dg / min. part One Part 2 .15 Fresh material 2.01 1.92 after 1 week 2.15 2.13 after 2 weeks 1.94 2.05 after 3 weeks 1.66 1.88 after 4 weeks 1.92 2.21 4 ° after 6 weeks 2.13 7.55

Equally significant was the fact that, after removal from the oven and further storage, with Room temperature, the granules of the preparation according to Part 2 were further degraded, while the Preparation granules according to Part 1 did not show any degradation under the same conditions. The results are summarized below:

Schmel / index, dg / min. I eil I Part 2 At distance 2.13 7.55 from the oven after I week 1.93 35.7 after 2 weeks 1.99 47.2

no Examples 34 to 40 show that with Applying a manufacturing process with several approaches to either these principles can be stored separately from one another or in the form of dry-mixed preparations for a long time without the

6s degradation reaction begins. A breakdown begins and takes place only then takes place when the individual basic approaches in hot form with each other to form homogeneous mixtures have been processed, or if at the beginning a

heat-processed, uniform preparation was produced.

Example 41

Degradable ethylene polymer preparations were made by placing them in hot form on a Roller frame various ethylene-ethyl acrylate copolymers of different ethyl acrylate content with 0.025% cobalt in the form of a cobalt octoate solution in Petroleum ether, different amounts of low molecular weight polypropylene wax than self-

Table X

IO oxidizing additive and 0.05% of the antioxidant A (Table IX) processed. For comparison purposes, a control containing no polypropylene was made. From these specimens, 0.25 mm thick plaques were depressurized, exposed to the weathering treatment, and the times after which surface cracks or failure of the samples occurred were recorded; the results are shown in Table X. All preparations according to the invention were degraded within a shorter time. A range is given if the degradation started within this period.

Crack formation after hours d Failure after hours C. approach Sowing / away C. 5 away 2 Polypropylene,% Polypropylene,% 0 1 2 0 I.

Ethyl acrylate content of the
Mixed polymer

1.7%

7.7%
12%
15%
18%
25%

200

> 75O 500
> 750 350

350

500

350

> 750

> 750
> 750

> 500

350 350

- »750 500 500

350 250-350

- »350 250 250-350

- »500-750 250

500 250

250-350 200 250

250
200

250

Example 42

There were ethylene polymer preparations made of LDPE (density 0.922), 0.5% polypropylene as self-oxidizing Additive and the amounts of solid iron (II) stearate and antioxidants listed below. The mixes were on melted in a two-roll mill, processed into foils and then granulated. The preparations became 0.5 mm thick plaques deformed, and all preparations containing iron salt were degradable, such as

Table XI

resulted from becoming brittle in the weathering test. The preparations can be molded too Objects such as B. pipes are extruded. Irrigation tubes made from these preparations do not need to be removed after the growing season, but can be plowed under because they gradually disintegrate into fine particles and mix with the soil. The preparations are shown in Table XI summarized.

preparation
ABC

E h

Eisend I) -stearal,% 0 0.1 0.15 0.25 0 0.1 0.15 0.25 0.1 0.25 0 0.1 0.15 0.25 0 0.1 0.15 0.25 0.1 0.25

Oxidation school / mittcl, %

Λ 0.02 0.02 0.03 0.05 0.02 0.02 0.03 0.05 0.04 0.1 0.02 0.02 0.03 0.05 0.02 0.02 0 , 03 0.05 0.04 0.1

C 0.04 0.04 0.06 0.1 0.04 0.04 0.06 0.1 0.08 0.2 0.04 0.04 0.06 0.1 0.04 0.04 0 , 06 0.1 0.08 0.2

UV stabilizer,%

i ^: - 0 0 C) 0 0.1 0.1 0.15 0.23 0.4 0.1 0 0 0 0 0.1 0.1 0.15 0.25 0.4 0.1

Titanium dioxide,% 0 0 0 0 0 0 0 0 0 0 2 2 2 2 2 2 2 2 2 2

Λ and C see Table IX.

Ii 2- (2'-llydr () xy-3'-terl.-luityl-5'-methylphenyl) -5-chlorobcivolria / ol.

Claims (4)

Claims; 1. Polymer preparation degradable by environmental influences, consisting of an ethylene polymer as a base resin, at least one self-oxidizing additive with at least one of one Hydrogen atom bonded to a carbon atom, which is more amenable to autoxidation than one to one normal secondary carbon atom bonded hydrogen atom, with at least one salt of at least one polyvalent transition metal with an atomic number of 21 to 30, 39 to 48 or 57 to 71 and an antioxidant for the ethylene polymer, the self-oxidizing Additive in an amount of 0.01 to 40 wt .-%, the salt of the polyvalent transition metal in an amount of 0.002 to 2.0 wt .-% (calculated as metal), and the antioxidant in one Amount of 0.0025 to 1 wt .-%, based in each case on the weight of the total preparation, is present. 2. Preparation according to claim 1, characterized in that the salt contains a polyvalent transition metal in which the electron transition in the 3d secondary shell or 4f secondary shell takes place. 3. A preparation according to claim 1, characterized in that it is an organic salt of a contains polyvalent transition metal. 4. Preparation according to claim 1, characterized in that it is a self-oxidizing low molecular weight Compound contains an unsaturated fatty acid.